EP0486592B1 - Fabrication de granules comprimes pour produits de lavage - Google Patents

Fabrication de granules comprimes pour produits de lavage Download PDF

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Publication number
EP0486592B1
EP0486592B1 EP90912777A EP90912777A EP0486592B1 EP 0486592 B1 EP0486592 B1 EP 0486592B1 EP 90912777 A EP90912777 A EP 90912777A EP 90912777 A EP90912777 A EP 90912777A EP 0486592 B1 EP0486592 B1 EP 0486592B1
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EP
European Patent Office
Prior art keywords
granules
weight
water
premix
bar
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP90912777A
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German (de)
English (en)
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EP0486592A1 (fr
Inventor
Franz-Josef Carduck
Hubert Pawelczyk
Wilfried Rähse
Jochen Jacobs
Eduard Smulders
Günther VOGT
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Priority claimed from DE19893926253 external-priority patent/DE3926253A1/de
Priority claimed from DE4010533A external-priority patent/DE4010533A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0486592A1 publication Critical patent/EP0486592A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the invention relates to a process for the production of compacted granules, the granules obtained by using the process and storage-stable and free-flowing detergent concentrates containing them and having a long shelf life.
  • German patent application 20 50 560 a process for the production of particulate detergents and cleaning agents ("pasta shape") with bulk weights between 500 and 900 g / l is known, in which a premix of a very specific composition is compressed "under pressure” and then extruded . No information was given regarding the amount of pressure to be applied. In order to prevent the strands from sticking together, they must be cooled by means of an air stream before they are then shredded into pieces of a certain length. The bulk density is inversely proportional to the length of the pieces.
  • German patent application 21 62 353 describes a process for the production of enzyme granules and detergent granules containing enzymes, which have a bulk density of between 300 and 1,000 g / l.
  • a mechanically pre-machined mass is pressed into a long strand under pressure, which is approximately between 7 and 35 bar.
  • they In order to prevent the threads from sticking together to form larger aggregates when they emerge from the extrusion press, they must be "deplastified". This is done either by cooling or by evaporating the moisture, the solvent or the plasticizer (surface hardening). Only then can the thread strands be broken into smaller sections of the desired length.
  • European patent application 351 937 describes a process for producing detergent and cleaning agent granules with bulk densities of at least 650 g / l, which in turn is dependent on the formulation.
  • Agents containing 12 to 70% by weight of surfactants must contain at least 15% by weight of water-soluble, crystalline inorganic salts, and the ratio of crystalline salt: surfactant must not be less than 0.4.
  • the agents are dry mixed and granulated in known mixers.
  • European patent application 352 135 describes a process for the production of granular detergents with bulk densities above 650 g / l, which assumes that a solid alkaline material is placed in a mixer or granulator with a cutting device and liquid anionic surfactant in the acid form does not exceed at temperatures 55 ° C is added so slowly that the mixture remains solid throughout the neutralization process.
  • the alkaline material must be used in excess. Only after complete neutralization can a liquid binder, for example water, liquid nonionic surfactant or an aqueous polycarboxylate solution, be added to the mixture. The granulation takes place in known mixers and granulators.
  • US Pat. No. 3,188,291 discloses the production of soap carriers and detergents in granular form with low bulk densities between approximately 16 and 480 g / l.
  • the mass is extruded at pressures between about 82 and 165 bar.
  • the mass was too viscous for prints beyond this and could no longer be extruded.
  • the bulk density was too high. This patent thus teaches that when using higher pressures during extrusion, low bulk densities are achieved, while when the pressure is reduced, the bulk density increases.
  • the object of the invention was to develop a process for the production of compacted granules which are used in detergents and cleaning agents and in particular in textile detergents and detergent concentrates.
  • the granules should be stable in storage and pourable and free-flowing.
  • the object was to provide a method which allows the shape of the individual, compacted granulate to be predetermined.
  • the invention accordingly relates to a first embodiment of the process for the production of compacted granules which are used in detergents and cleaning agents.
  • a homogeneous, solid, free-flowing premix is extruded in the form of a strand with the addition of a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined granule size at high pressures between 25 and 200 bar.
  • the strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device.
  • the application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands.
  • the premix consists at least in part of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, which may contain liquid constituents are mixed.
  • the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.
  • liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in.
  • aids are of polyfunctional importance in the context of the invention.
  • they enable the formation of the primary granulate by causing the premix to be converted into a mass which can be pressed under high pressure, and, if desired, subsequent shaping processing, which in particular consists of rounding off the primarily formed granule.
  • subsequent shaping processing which in particular consists of rounding off the primarily formed granule.
  • they contribute to the stability of the granulate, they maintain its predetermined spatial shape, in particular when mixing with other components, if necessary, during filling, during transport and storage of the granules, and in particular prevent the formation of undesirable dust-like components.
  • the auxiliaries discussed here can have an intrinsic effect in the washing and cleaning process, in particular in interaction with other mixture components.
  • plasticizers and / or lubricants used as auxiliaries can be flowable, gel-like or pasty at room temperature without the need to use an additional liquid phase.
  • Preferred plasticizers and / or lubricants are preparations based on surfactant components and / or based on water-soluble or water-emulsifiable or water-dispersible polymer compounds. Examples of a plasticizer and / or lubricant that can be used without the use of an additional liquid phase are numerous types of the nonionic surfactants commonly used in detergents and cleaning agents.
  • plasticizers and / or lubricants are used which have been produced using limited amounts of auxiliary liquids.
  • Organic liquid phases which are water-soluble or water-miscible are preferably used here.
  • aqueous preparations of the plasticizers and / or lubricants are preferred.
  • the surfactants and / or polymer compounds used as plasticizers and / or lubricants are advantageously introduced into the process in such a concentrated form that the nature of the plastic, slidably compressible mass can be adjusted even with small amounts of these auxiliaries.
  • the pastes are preferably used in amounts not exceeding 12% by weight, in particular in amounts between 0.5 and 10% by weight, and particularly advantageously between 3 to 8% by weight, based on the mixture as a whole. At least 30% by weight, preferably at least 40% by weight pastes and gels are particularly suitable.
  • surfactant preparations with a surfactant content of at least 50% by weight, in particular from 50 to 70% by weight, are used.
  • the invention takes advantage of the fact that, in particular, these highly concentrated aqueous surfactant mixtures show a state that is in the form of a paste or gel Lubricant character can be called.
  • the surfactant components thus introduced form cover and intermediate layers which act like binders and which are jointly responsible for the grain cohesion.
  • Anionic surfactant salts in particular sulfates and sulfonates, from the wide range of the compounds proposed here for detergents and cleaning agents, optionally in admixture with customary nonionic compounds, can be of particular importance here.
  • a mixture of at least two powder components tower powder / carrier bead
  • sodium perborate monohydrate and / or tetrahydrate
  • Equally preferred is the use of 3 to 8% by weight of a 50 to 60% by weight aqueous paste of an alkyl polyglycoside (APG) of the general formula RO (G) x , in which R is a primary straight-chain or in 2 Position methyl-branched aliphatic radical with 8 to 22, preferably 8 to 18 carbon atoms, G is a symbol which represents a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.
  • APG alkyl polyglycoside
  • plasticizers and / or lubricants based on surfactants are mixtures of ABS and APG pastes, as well as mixtures of ABS pastes and ethoxylated C8-C18 fatty alcohols, mixtures of ethoxylated fatty alcohols and water and mixtures of APG: ethoxylated fatty alcohol: water in a ratio of 0.5-1: 1-1.5: 1, in which case the APG content is calculated as an active substance and not as a paste.
  • polymer compounds in numerous washing and cleaning agents is common today, since the polymer compounds act, for example, as builders with the ability to bind water hardness.
  • polymers containing carboxyl groups which are also in the salt form, for. B. present as an alkali salt can, like the sodium or potassium salts of homopolymeric or copolymeric polycarboxylates, for example polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, acrylamide or methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, acrylamide or methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
  • polymer compounds are also used to improve the dirt-carrying capacity of an aqueous washing liquor. Examples include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).
  • aqueous preparation forms of these polymer compounds are distinguished by a pronounced lubricating character which gives the decisive processing aid in the process according to the invention.
  • these polymer components dry out to polymer films which, on the one hand, promote the cohesion of the granules and, on the other hand, easily change back to the state of solution or emulsification or dispersion when added in aqueous media in particular.
  • a polymer in particular a copolymer of acrylic acid and maleic acid
  • a plasticizer and / or lubricant it is particularly preferred to use 3 to 8% by weight of a 30 to 50% by weight solution of a polymer, in particular a copolymer of acrylic acid and maleic acid, in water as a plasticizer and / or lubricant.
  • a polymer in particular a copolymer of acrylic acid and maleic acid
  • surfactant in particular anionic surfactant, plasticizers and / or lubricants are also advantageous.
  • plasticizers and / or lubricants include gelatin, starch and starch derivatives and polyvinyl alcohol.
  • liquid phase (s) are used that, when mixed simply, a free-flowing, powdery structure of the premix is retained even after the addition of the plasticizer and / or lubricant.
  • the content of free water not bound as crystal water or in comparable form in the respective substance mixture in this processing stage is preferably up to 12% by weight, preferably up to 10% by weight and in particular in the range from about 4 to 8% by weight. %. Included in this amount is the amount of water that is entered via the lubricating plasticizer.
  • further solids can also be added to the premix after the addition of the plasticizer and / or lubricant.
  • the total mass is briefly mixed in, resulting in a solid, free-flowing premix which is suitable for feeding a homogenization system.
  • Kneaders of any configuration for example twin-screw kneaders, can preferably be selected as the homogenizing device.
  • this homogenization step it may be expedient in this homogenization step to maintain reliable temperature control of the mixture to be processed, in individual cases the composition of the mixture for the respectively optimal temperature range can be a determining factor.
  • the intensive mixing process can in itself lead to the desired temperature increase. Moderately elevated temperatures of, for example, a maximum of about 60 to 70 ° C. are generally not exceeded.
  • processing temperature-sensitive substances - for example perborate compounds - compliance with lower temperatures (for example about 40 to 45 ° C.) can be advantageous.
  • the premix is mixed and kneaded so intensively that the previously solid and dry mixture is worked up to the compacted, plasticized and form-compressible mass becomes. At the same time, the cutting ability of the homogenized mixture is ensured.
  • the free-flowing premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C.
  • the premix is compressed, plasticized at pressures from 50 to 180 bar, in particular at pressures from 80 to 180 bar, extruded in the form of fine strands through the perforated die plate in the extruder head, and finally, preferably by means of a rotating knives, preferably to spherical bis cylindrical granules crushed.
  • the hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule size.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • Absolute particle sizes can be, for example, in the range from a few tenths of a millimeter to a few centimeters, for example in the range from about 0.3 mm up to 1 to 2 cm. In general, however, particle diameters of up to at most 0.8 cm will be preferred.
  • Important embodiments of the invention provide for the production of the uniform granule grain with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1.
  • the granulation in this first homogenizing process step is, however, not restricted to the processing of the plasticized premix via extruder screws and perforated plates of the type described, which are arranged in the extruder head. Also by similar, conventional granulating devices, for example pellet presses, 1- and 2-shaft extruders, planetary roller extruders, plasticized, compressed and homogenized mixtures of substances can be granulated into granular material according to the invention.
  • the still plastic, moist primary granulate is first fed to a further shaping processing step.
  • the edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained.
  • Dry powders suitable for detergents and cleaning agents can be pulverulent materials or corresponding inert materials.
  • a particularly useful material in this connection is, for example, zeolite powder such as zeolite NaA powder.
  • This final shaping of the still moist granulate from the extruder granulation can be carried out batchwise or continuously in standard rounding machines.
  • Corresponding rounding devices with a rotating base plate are suitable, for example, the desired degree of rounding being able to be set by varying the granulate residence time in the rounding device and / or the speed of rotation of the device plate.
  • the finally shaped granulate is preferably fed to a drying step, for example a fluidized bed dryer, in which, at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set, but then also not be crossed, be exceeded, be passed.
  • a drying step for example a fluidized bed dryer, in which, at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set, but then also not be crossed, be exceeded, be passed.
  • the product is cooled with cold air, for example.
  • Preferred residual amounts of unbound water are up to about 1% by weight, preferably in the range from about 0.1 to 0.5% by weight.
  • the resulting very low-dust Product can be classified to remove small coarse particles formed, for example, sieved.
  • the grain proportion to be set according to the invention is generally above 90%, preferably above 95%, of the granulated material.
  • the "internal drying" of the granules is also possible: by using moisture-binding constituents in the premix, the plasticizing effect of the liquid components present can be exploited in the short processing time; then, by binding at least partial portions of these liquid portions through the mixed-in components, the granules are dried "from the inside out", so that the external drying can be shortened or omitted entirely.
  • Components which are able to bind water in the form of water of crystallization are, for example, sodium sulfate and / or sodium carbonate in anhydrous or low-water form or else a zeolite partially freed from water of crystallization.
  • the primarily formed and still plastic granules can be loaded with further active ingredients before, during and / or after any rounding that may have been carried out.
  • sensitive, in particular temperature-sensitive, formulation constituents can also be added to the dried granulate, e.g. B. sprayed and / or mixed as a separately formed grain to form a multigrain mixture.
  • the invention with its granules produced in a novel manner, covers both the area of ready-to-use multi-substance mixtures in the form of uniform granules and also partial products which, in order to complete the formulation, still mix with other constituents of the detergent and cleaning agent concerned need.
  • more than 60% by weight and in particular more than 70% by weight of the total mixture of substances are granules obtained by the process according to the invention with a highly compressed and solid grain structure.
  • granule systems are used which represent a combination of granules of different compositions.
  • the storage-stable combination of potentially reactive or at least only partially compatible components is achieved.
  • An example of this are common textile detergents, which, however, now use at least two types of granules in a mixture with one another in the new preparation form.
  • the bleaching agent component in particular perborate and sodium carbonate containing water of crystallization, is pelletized with the use of a proportion of the plasticizers and / or lubricants, in a separate second granulate the zeolite used as detergent builder substance, in particular zeolite NaA, is pressed together with the rest of the detergent components .
  • the zeolite used as detergent builder substance in particular zeolite NaA
  • the granules according to the invention can be recycled, i.e. they can be used in the first process step in combination with other substances to produce the plasticized premix.
  • the material densities in the grain and thus also the bulk density of the granules are largely determined by the working pressures used when the homogenized material is pressed through the perforated plates.
  • Bulk weights in the range from 850 to 980 g / l can be set on the basis of commercially available textile detergent formulations, with good free-flowing properties and a preferably homogeneous, spherical grain structure.
  • free-flowing granules in the dry state with uniform bulk weights of 950 to 980 g / l have been realized with an average particle size of the spherical granules in the range of approximately 1 mm.
  • the method according to the invention is characterized by a very low proportion of returned goods.
  • the proportion of return material after sieving the granulate through a 1.6 mm sieve was in the range of at most 3%.
  • sensitive formulation components for example activators for bleaches, enzymes, defoamers, in particular silicone defoamers, perfume and the like - can be added to the granules. Even then, detergent products with bulk weights in the range of about 900 g / l are still obtained.
  • the textile detergents which are customary on the market today in the form of free-flowing powders and / or granules generally contain a combination of anionic-surfactant and non-surfactant active detergent components.
  • the anionic surfactant components make up the larger proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture.
  • the total surfactant content for powdery, free-flowing household detergents is about 12 to a maximum of 15% by weight, based on the total detergent. This also applies to the detergents with increased bulk density that are currently on the market.
  • the invention allows the use of the described method for the production of detergent concentrates, in particular corresponding concentrates, which are essentially non-sticky, free-flowing and free-flowing, storage-stable for textile detergents with a significantly increased content of detergent surfactants.
  • Textile detergent concentrates with surfactant contents of up to about 35% by weight and preferably in the range from about 15 to 25% by weight can be produced without the fear of sticking and / or product softening, as would be the case with such an increase in the powdery mixtures available on the market of the surfactant content occur.
  • the goal of space-saving and low-packaging detergent preparations is optimally achieved without leaving the field of free-flowing, stable storage detergent preparations and fulfilling all other requirements to have to.
  • the bleach in particular sodium perborate in the form of the monohydrate and / or the tetrahydrate
  • the bleach can already be processed in the raw material to be plasticized and then pressed, without substantial losses of perborate occurring.
  • Each granulate thus contains the predetermined percentage of perborate.
  • Spray-dried powders with variable admixtures can be used.
  • neither spray-dried powders nor pre-formed powders with a bead structure are required to produce the raw materials to be pressed.
  • the use or addition of heavy powder of the individual raw materials is not necessary.
  • the processing of the nonionic surfactants usually used in detergents and cleaning agents becomes problem-free, and the pluming problems that usually occur in spray drying are eliminated.
  • the nonionic surfactants are easily added by incorporation into the mixture before extrusion, they can even be used here highly concentrated aqueous gel or paste provide valuable process help in the manner described.
  • the invention relates to universal detergents for textiles which are present in the new form of the free-flowing granules with bulk densities above 750 g / l, in particular above 800 g / l, for example in the range from 850 to 950 g / l and in a particularly important one
  • Embodiment are characterized by a uniform particle shape and size.
  • the preferred particle shape is spherical.
  • Preferred particle sizes here are in the range from about 0.5 to 5 mm ball diameter, in particular in the range from about 0.8 to 2 mm.
  • the type and quantity of the recipe components can correspond to that of today's textile detergents containing builders.
  • the following is general information on the composition of suitable active substance mixtures, the components of textile detergents which are common today, in particular, being summarized here.
  • Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (C9-C15-alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C12-C18 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent or acid hydrolysis of the Receives sulfonation products.
  • dialcan sulfonates which are obtainable from C12-C18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable sulfate type surfactants are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, i.e. H. from fatty alcohols, e.g. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C10-C20 oxo alcohols, and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl branched C9-C11 alcohols with an average of 3.5 moles of ethylene oxide, are suitable.
  • Sulfated fatty acid monoglycerides are also suitable.
  • soaps from natural or synthetic preferably saturated fatty acids.
  • natural fatty acids such.
  • B. coconut, palm kernel or tallow fatty acid derived soap mixtures Preferred are those which are composed of 50 to 100% of saturated C12-C18 fatty acid soaps and 0 to 50% of oleic acid soap.
  • anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the content of anionic surfactants or anionic surfactant mixtures in detergents according to the invention is preferably 5 to 40, in particular 8 to 30,% by weight.
  • water-soluble nonionics In addition to the water-soluble nonionics, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
  • alkyl glycosides of the general formula RO- (G) x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18 C atoms, methyl-branched in the 2-position, G is a symbol is a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.
  • Suitable and, in particular, ecologically harmless builder substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837) find a preferred use.
  • Their average particle size is usually in the range from 1 to 10 »m (measurement method: Coulter Counter, volume distribution).
  • Their content is generally 0 to 40, preferably 10 to 30% by weight, based on the anhydrous substance.
  • Zeolite NaA is produced in the form of a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents.
  • the zeolite or at least zeolite fractions to the premix in the form of the undried masterbatch or a material which has only partially dried and is therefore only limited in its water content.
  • builder components which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, in which the proportion of acid is at least 50%.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.
  • Usable organic builders are, for example, the polycarboxylic acid preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.
  • NTA nitrilotriacetate
  • phosphates can also be used, in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for lime salts.
  • the phosphate content based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.
  • Suitable inorganic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as "washing alkalis"; Of the alkali silicates, especially the sodium silicates with a Na2O: SiO2 ratio of 1: 1 to 1: 3.5 can be used.
  • the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone is also useful.
  • Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. B. of sulfates and / or sulfonates with nonionics and / or with soaps. Soap rises the foam-suppressing effect with the degree of saturation and the C number of the fatty acid residue. Soaps of natural and synthetic origin are suitable as foam-inhibiting soaps, which have a high proportion of C1 e-C24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bisacylamides derived from C12-C20 alkylamines and C2-C6 dicarboxylic acids are also useful.
  • Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizer and / or lubricant.
  • bleaching agents which supply H2O2 in water
  • sodium perborate tetrahydrate (NaBO2. H2O2. 3 H2O) and sodium perborate monohydrate (NaBO2. H2O2) are of particular importance.
  • Other usable bleaching agents are, for example, peroxy carbonate (Na2CO3. 1.5 H2O2), peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic acid anhydrides and esters of polyols, such as Glucose pentaacetate.
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • B salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or Compounds of the same structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. B. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and aminotrimethylenephosphonic acid (ATP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) come into consideration as stabilizers, in particular for per-compounds and enzymes.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ATP aminotrimethylenephosphonic acid
  • DTPMP or DETPMP diethylenetriamine-pentamethylenephosphonic acid
  • the first mixture component was a spray-dried powder (tower powder) based on the following main components: Surfactant mixture I 17.5% by weight calcined soda 35% by weight Zeolite NaA, anhydrous substance 22% by weight Acrylic acid copolymer (Sokalan CP5 (R) ) 10% by weight Water, bound 8.2% by weight Water, free 1.8% by weight the rest of the usual detergent additives
  • Surfactant mixture I consisted of sodium dodecylbenzenesulfonate (ABS) and tallow fatty alcohol reacted with 5 ethylene oxide groups (EO) in a ratio of 11.5: 1.
  • the second mixture component was a carrier bead containing non-surfactant, which was composed of the following main components: C12-C18 fatty alcohol with 5 EO 22% by weight Zeolite NaA, anhydrous substance 55% by weight Acrylic acid copolymer (Sokalan CP5 (R) ) 3% by weight Water, bound 14.5% by weight Water, free 1.3% by weight the rest sodium sulfate and other usual auxiliary substances
  • the free-flowing material thus obtained was fed to the homogenizing compression and plasticization.
  • the mass formed was extruded in the form of a strand, chopped into cylindrical granulate particles, rounded off and dried.
  • the tower powder (TP) and the carrier bead (TB) were placed in a batch mixer (20 liters) equipped with a cutter head shredder and 0.5 min. mixed. With the mixer and cutter head chopper running, the required amount of water and then the entire ABS paste was pumped in via a slot nozzle (2.5 min.). Finally, if necessary, the entire amount of Na perborate monohydrate was added and 1 min. mixed. The resulting premix was free-flowing and could be used to feed the continuous kneader-extruder system.
  • the premix obtained was fed continuously to a 2-screw kneader (extruder), the housing of which, including the extruder pelletizing head, was heated to about 45 to 50 ° C. Under the shear of the extruder screws, the premix was plasticized and then extruded through the extruder head perforated die plate into fine strands (1.0 and 1.2 mm in diameter), which were chopped into cylindrical granules (length / diameter Ratio about 1, hot tee).
  • extruder 2-screw kneader
  • the warm and moist granules obtained from the extruder granulation were rounded off batchwise or continuously in a commercially available rounding machine of the Marumerizer type with the addition of zeolite NaA powder as a powdering agent.
  • the desired degree of rounding was set by varying the granulate dwell time in the rounding device and the speed of rotation of the device disc.
  • the moist granules from the rounding device were dried in a discontinuously operating fluidized bed dryer at a supply air temperature of 75 to 80 ° C. to a product temperature of 55 to 60 ° C. for 15 minutes. After the product had been cooled to 30 ° C. with cold air, a free-flowing product was obtained.
  • the very low-dust product was sieved through a sieve with a mesh size of 1.6 mm.
  • the proportion of return material above 1.6 mm was in the range of maximum 3% in all cases.
  • the sieved gut grain was used as the basis for the blending of detergent end products.
  • a tower powder (ABS 9%, calcined soda 25%, zeolite NaA (anhydrous substance) 38%, acrylic acid copolymer 8%, water 15%, the rest of the usual detergent components) was used in an amount of 88 , 5 wt .-% with 2.5 wt .-% water, 5 wt .-% nonionic surfactant based on C12-C18 fatty alcohol ⁇ 5 EO and 4 wt .-% 55% ABS Na paste and worked up.
  • Free-flowing granules with a bulk density of 950 g / l were obtained.
  • Free-flowing tower powder based on the following main components: 22% by weight of surfactant mixture I, 2.5% by weight of sodium soap based on sebum, 15% by weight of calcined soda, 7% by weight of water glass, 26.5% by weight % Zeolite NaA (anhydrous substance), 7.5% by weight acrylic copolymer, 12% by weight water, the rest of the usual co-formulants.
  • Carrier bead based on the following main components: 22% by weight C12-C18 fatty alcohol ⁇ 5 EO, tallow-based Na soap 2% by weight, Zeolite NaA (anhydrous substance) 55% by weight, acrylic acid copolymer 3% by weight, water 15% by weight.
  • the comminuted and mixed material according to the working instructions from Examples 1 to 5 was mixed with approximately 11% by weight (based on the total mixture) of 60% ABS paste and homogenized.
  • the resulting material was plasticized by kneading and pressed to give shape. Free-flowing granules in the form of spheres with bulk densities in the range from 900 to 950 g / l were obtained which were stable in storage (storage time: 1 year).
  • a phosphate-free and pH-neutral tower powder with the following composition Surfactant mixture I 16% by weight Soap 2.8% by weight Zeolite 16.0% by weight Sokalan CP 5 (R) 3.2% by weight Na2SO4 58% by weight
  • the rest of the usual small components was intensively mixed with 5% by weight ABS paste (40%) and then first plasticized in an extruder and then extruded through a perforated disk with 1.2 mm nozzle bores. The temperature was controlled by tempering the jacket in such a way that product temperatures of 45 to 50 ° C. were established.
  • the compressed mass strands emerging from the nozzle plate were cut off by rotating knives and cylindrical particles with a length / diameter ratio of approx. 1 were obtained.
  • the still warm particles were rounded in a Marumerizer with the addition of 2% by weight of zeolite NaA powder and dried in a fluidized bed dryer as described above. After drying, products with bulk densities between 850 - 920 g / l were obtained - the respective bulk density was dependent on the extent of the rounding.
  • ABS 12.5% by weight ABS and 7.5% by weight C12-C18 fatty alcohol ⁇ 5 EO, 25% by weight soda, 40% by weight zeolite (anhydrous substance) and 12% by weight % bound water and several small components were prepared in a mixer and then sprayed with 5% by weight of a 55% ABS paste, based on the sum of the mixture and ABS paste.
  • the premix prepared as described above was introduced into the annular space of the pellet press via a screw conveyor.
  • the press consisted of a rotating wooden roller into which radial holes were made, distributed over the entire circumference. A press roll was arranged eccentrically in this ring die. In this experiment, a ring die with a diameter of approx. 80 mm and approx. 500 holes was used. The bore diameter was 1.5 mm.
  • a continuous feeding of the product was achieved through the screw dosing.
  • the product was compacted in the gap between the roller and the die.
  • the pressure defined by the extrudability of the mass was reached, the product was pressed through the radial channels of the die and the entire strand was pushed out by the appropriate length.
  • the strand was cut to a length of 1.5 mm by a knife attached to the outside of the die.
  • the cylindrical granules produced in this way were rounded off in a further process step.
  • the strength of the granules could be improved by adding 3% by weight of zeolite NaA in the rounding step.
  • Abrasion-resistant and very free-flowing granules with a bulk density of the dry products of 950 g / l were obtained.

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Claims (11)

  1. Procédé de fabrication de granulés compactés, qui sont utilisés dans les agents de lavage et de nettoyage, dans lequel un prémélange homogène, additionné d'un plastifiant et/ou d'un lubrifiant, est comprimé sous pression, via des moules perforés présentant des ouvertures d'orifice de la dimension prédéterminée des granulés, caractérisé en ce qu'un prémélange homogène, solide et coulant est comprimé sous forme de boudins, à des pressions élevées comprises entre 25 et 200 bars et en ce que le boudin est débité à la dimension prédéterminée des granulés, à l'aide d'un dispositif de coupe, après sa sortie du moule perforé.
  2. Procédé selon la revendication 1, caractérisé en ce que la pression se situe entre 30 et 200 bars, en particulier entre 50 et 180 bars et en ce que le grain de granulé homogène présente un diamètre de 0,5 à 5 mm et, en particulier de 0,8 à 3 mm.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on met en oeuvre comme plastifiant et/ou comme lubrifiant, des préparations coulantes, geliformes ou pâteuses à base de tensioactifs anioniques ou non ioniques, de composés polymères solubles, émulsifiables ou dispersibles dans l'eau, ou de mélanges de ceux-ci, des pâtes ou des solutions aqueuses hautement concentrées étant préférées.
  4. Procédé selon la revendication 3, caractérisé en ce que l'on met en oeuvre comme plastifiant et/ou comme lubrifiant, des pâtes tensioactives aqueuses en proportions de 0,5 à 10 % en poids.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le prémélange obtenu sous adjonction du plastifiant et/ou du lubrifiant présente une concentration en eau libre, non fixée comme eau de cristallisation ou sous une forme similaire, pouvant atteindre 10 % en poids et, en particulier, comprise entre 4 et 8 % en poids.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que sont appropriés comme dispositif d'homogénéisation, des appareils de granulation usuels, tels que presses à pellets, extrudeuses à 1 et 2 arbres et extrudeuses planétaires, une extrudeuse à double vis fonctionnant en continu, dont l'enveloppe et la tête de granulation sont thermostatisées à la température d'extrusion prédéterminée étant préférée.
  7. Procédé selon la revendication 6, caractérisé en ce que le prémélange coulant est compacté et plastifié entre 50 et 180 bars, sous l'action de cisaillement des vis d'extrusion, extrudé dans la tête d'extrusion, sous la forme de fins boudins, via le corps de filière perforé, dont le diamètre des perforations est adapté à la dimension de granulé sélectionnée, et en ce que le produit d'extrusion est broyé à l'aide d'un couteau d'abattage rotatif en grains de granulés sphériques à cylindriques, présentant un rapport longueur/diamètre d'environ 1:1 à 3:1, et en ce que ce granulé primaire humide, encore plastique est arrondi dans un appareil d'arrondissage usuel, moyennant la co-utilisation de quantités limitées de poudre sèche, de préférence de la zéolithe NaA.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la co-utilisation dans le prémélange de constituants fixant l'humidité, de préférence du sulfate de sodium, du carbonate de sodium et/ou de la zéolithe, sous forme anhydre ou pauvre en eau, provoque un séchage interne au moins partiel du granulé, par fixation de fractions au moins partielles des quantités de liquide présentes, de sorte qu'il est possible d'abréger voire de supprimer le séchage extérieur, qui est réalisé de préférence dans un séchoir à lit fluidisé à des températures d'air amené modérément élevées jusqu'à 80° C au maximum et à des températures de produit modérées en conséquence de 55 à 60 °C.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que les grains de granulés primaires encore plastiques sont soumis à l'action d'autres substances avant, pendant et/ou après un éventuel arrondissage, les ingrédients thermosensibles en particulier étant additionnés au granulé séché, pulvérisés sur celui-ci et/ou mélangés avec celui-ci comme grain formé séparément, en formant un mélange à grains multiples.
  10. Granulé, obtenu selon l'une des revendications 1 à 9, caractérisé en ce qu'il possède une densité en vrac supérieure à 700 g/l, de préférence de 750 à 1000 g/l et en particulier, de 850 à 980 g/l et qu'il se présente comme un mélange complexe prêt à l'emploi, sous la forme de granulés homogènes, comme association de granulés de composition différente ou comme un produit partiel devant encore être mélangé avec d'autres ingrédients d'agents de lavage et de nettoyage usuels pour que la formulation soit complète.
  11. Produits de lavage et de nettoyage, renfermant des granulés selon la revendication 10, caractérisé en ce qu'ils contiennent une concentration accrue de tensioactifs jusqu'à 35 % en poids, de préférence comprise entre 15 et 25 % en poids.
EP90912777A 1989-08-09 1990-07-31 Fabrication de granules comprimes pour produits de lavage Expired - Lifetime EP0486592B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19893926253 DE3926253A1 (de) 1989-08-09 1989-08-09 Verdichtete wasch- und reinigungsmittel in granulatform, verfahren zu ihrer herstellung und anwendung des verfahrens zur gewinnung lagerstabil rieselfaehiger waschmittel-konzentrate
DE3926253 1989-08-09
DE4010533 1990-04-02
DE4010533A DE4010533A1 (de) 1990-04-02 1990-04-02 Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
PCT/EP1990/001247 WO1991002047A1 (fr) 1989-08-09 1990-07-31 Fabrication de granules comprimes pour produits de lavage

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EP0486592A1 EP0486592A1 (fr) 1992-05-27
EP0486592B1 true EP0486592B1 (fr) 1994-06-15

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JP (1) JPH05500076A (fr)
KR (1) KR927003783A (fr)
AT (1) ATE107352T1 (fr)
DE (1) DE59006160D1 (fr)
DK (1) DK0486592T3 (fr)
ES (1) ES2055441T3 (fr)
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US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US7888104B2 (en) 2000-11-28 2011-02-15 Henkel Ag & Co. Kgaa Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase
WO2002053697A1 (fr) * 2001-01-08 2002-07-11 Reckitt Benckiser N.V. Methode de production de produits de nettoyage
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US7510859B2 (en) 2002-12-20 2009-03-31 Henkel Kommanditgesellschaft Auf Aktien Subtilisin variants with improved perhydrolase activity
DE102004047777B4 (de) 2004-10-01 2018-05-09 Basf Se Alpha-Amylase-Varianten mit erhöhter Lösungsmittelstabilität, Verfahren zu deren Herstellung sowie deren Verwendung
DE102004047776B4 (de) 2004-10-01 2018-05-09 Basf Se Gegen Di- und/oder Multimerisierung stabilisierte Alpha-Amylase-Varianten, Verfahren zu deren Herstellung sowie deren Verwendung
US8263541B2 (en) 2005-08-19 2012-09-11 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
US8785362B2 (en) 2005-08-19 2014-07-22 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit

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WO1991002047A1 (fr) 1991-02-21
DE59006160D1 (de) 1994-07-21
US5318733A (en) 1994-06-07
EP0486592A1 (fr) 1992-05-27
KR927003783A (ko) 1992-12-18
ATE107352T1 (de) 1994-07-15
JPH05500076A (ja) 1993-01-14
DK0486592T3 (da) 1994-07-18
ES2055441T3 (es) 1994-08-16

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